Producing BDO via hydroformylation of allyl alcohol made from glycerin

Abstract

A method including hydroformylating, with syngas, allyl alcohol in an allyl alcohol feed, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; and producing a 1,4-butanediol (BDO) product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product. A method including hydroformylating, with syngas, allyl alcohol in a feed comprising bio-allyl alcohol, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; and producing a BDO product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product. A method including hydroformylating, with syngas, bio-allyl alcohol in a feed comprising bio-allyl alcohol, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde and 3-hydroxy-2-methylpropionaldehyde; producing a BDO product comprising BDO and 1,3-methylpropanediol via hydrogenation of at least a portion of the hydroformylation product; and removing a byproduct of the production of the bio-allyl alcohol prior to hydroformylating the bio-allyl alcohol and/or from the BDO-product.

What is claimed is: 
     
       1. A method comprising:
 producing allyl alcohol from glycerin in the presence of 0.5 to 10 mole percent of a rhenium catalyst, wherein the rhenium catalyst is selected from the group consisting of rhenium dioxide, methyltrioxorhenium (MTO), rhenium trioxide and a combination thereof, 
 hydroformylating, with synthesis gas, allyl alcohol in a feed comprising allyl alcohol derived from glycerin, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde (HBA) and 3-hydroxy-2-methylpropionaldehyde (HMPA) in a ratio of HBA:HMPA of at least 11.5:1; and 
 producing a 1,4-butanediol (BDO) product comprising BDO and 1,3-methylpropanediol (MPD) via hydrogenation of at least a portion of the hydroformylation product. 
 
     
     
       2. The method of  claim 1 , wherein the feed comprises bio-allyl alcohol derived from bio-based glycerin, non-bio-allyl alcohol derived from non-bio-based glycerin, or a combination thereof. 
     
     
       3. The method of  claim 1 , wherein the feed comprising allyl alcohol further comprises acrolein, lactic acid, octene isomers, or a combination thereof, and wherein the method further comprises removing acrolein, lactic acid, octene isomers, or a combination thereof from the feed prior to hydroformylating the allyl alcohol, from the BDO-product, or both. 
     
     
       4. The method of  claim 1 , wherein hydroformylation is performed in anhydrous toluene, with a rhodium catalyst in the presence of phosphine ligands, or both. 
     
     
       5. The method of  claim 4 , wherein the hydroformylation is performed in the presence of a catalyst solution comprising a rhodium catalyst comprising Rh(CO) 2 (acac) and one or more phosphine ligands. 
     
     
       6. The method of  claim 5 , wherein the one or more phosphine ligands comprise a diphosphine, and wherein the molar ratio of Rh(CO) 2 (acac) to the diphosphine ligands is from 0.1:1 to 1:5. 
     
     
       7. The method of  claim 4 , wherein the hydroformylation is carried out at a pressure in the range of from 20 psig to 600 psig, and a temperature in the range of from 35° C. to 120° C. 
     
     
       8. The method of  claim 1 , wherein the hydroformylation product further comprises one or more byproducts selected from C3 products, including n-propanol, propionaldehyde, and combinations thereof, and wherein a sum total amount of the one or more byproducts is less than or equal to 0.5 mole percent. 
     
     
       9. The method of  claim 1 , wherein the synthesis gas comprises a molar ratio of carbon monoxide to hydrogen in the range of from 0.5:1.5 to 1.5:0.5. 
     
     
       10. The method of  claim 1  further comprising producing at least a portion of the allyl alcohol in the feed comprising allyl alcohol by exposing glycerin to a temperature of greater than 140° C. in the presence of the rhenium catalyst to produce a product comprising allyl alcohol. 
     
     
       11. The method of  claim 10 , wherein the rhenium catalyst is present in an amount ranging from 3 to 10 mole percent, and wherein the feed comprising allyl alcohol contains less than 1.0 mole percent of octene isomers per mole of allyl alcohol. 
     
     
       12. A method comprising:
 producing bio-allyl alcohol from bio-glycerin in the presence of 0.5 to 10 mole percent of a rhenium catalyst, wherein the rhenium catalyst is selected from the group consisting of rhenium dioxide, methyltrioxorhenium (MTO), rhenium trioxide and a combination thereof, 
 hydroformylating, with synthesis gas, allyl alcohol in a feed comprising bio-allyl alcohol derived from bio-glycerin, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde (HBA) and 3-hydroxy-2-methylpropionaldehyde (HMPA) in a ratio of HBA:HMPA of at least 11.5:1; and 
 producing a 1,4-butanediol (BDO) product comprising BDO and 1,3-methylpropanediol (MPD) via hydrogenation of at least a portion of the hydroformylation product. 
 
     
     
       13. The method of  claim 12  further comprising producing at least a portion of the bio-allyl alcohol in the feed by exposing bio-glycerin to a temperature of greater than 140° C. in the presence of a catalyst to produce a product comprising bio-allyl alcohol. 
     
     
       14. The method of  claim 13 , wherein the rhenium catalyst is present in an amount ranging from 2.5 to 7.5 mole percent, and wherein the feed comprising bio-allyl alcohol contains less than 1 mole percent of octene isomers per mole of bio-allyl alcohol. 
     
     
       15. The method of  claim 13 , wherein the bio-glycerin is exposed to a temperature of greater than 140° C. in the presence of a solvent. 
     
     
       16. A method comprising:
 producing bio-allyl alcohol from bio-glycerin in the presence of 0.5 to 10 mole percent of a rhenium catalyst, wherein the rhenium catalyst is selected from the group consisting of rhenium dioxide, methyltrioxorhenium (MTO), rhenium trioxide and a combination thereof, 
 hydroformylating, with synthesis gas, bio-allyl alcohol in a feed comprising bio-allyl alcohol derived from bio-glycerin, to produce a hydroformylation product comprising 4-hydroxybutyraldehyde (HBA) and 3-hydroxy-2-methylpropionaldehyde (HMPA) in a ratio of HBA:HMPA of at least 11.5:1; 
 producing a 1,4-butanediol (BDO) product comprising BDO and 1,3-methylpropanediol (MPD) via hydrogenation of at least a portion of the hydroformylation product; and 
 removing a byproduct of the production of the bio-allyl alcohol prior to hydroformylating the bio-allyl alcohol, from the BDO-product, or both. 
 
     
     
       17. The method of  claim 16 , wherein the byproduct comprises acrolein, lactic acid, octene isomers, or a combination thereof. 
     
     
       18. The method of  claim 16  further comprising producing at least a portion of the bio-allyl alcohol in the feed by exposing bio-glycerin to a temperature of greater than 140° C. in the presence of the rhenium catalyst to produce a product comprising bio-allyl alcohol. 
     
     
       19. The method of  claim 18 , wherein the rhenium catalyst is present in an amount ranging from 2.5 to 7.5 mole percent. 
     
     
       20. The method of  claim 18 , wherein the bio-glycerin is exposed to a temperature of greater than 140° C. in the presence of a solvent.